CN102199274A - Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof - Google Patents
Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof Download PDFInfo
- Publication number
- CN102199274A CN102199274A CN 201110092642 CN201110092642A CN102199274A CN 102199274 A CN102199274 A CN 102199274A CN 201110092642 CN201110092642 CN 201110092642 CN 201110092642 A CN201110092642 A CN 201110092642A CN 102199274 A CN102199274 A CN 102199274A
- Authority
- CN
- China
- Prior art keywords
- reaction
- original position
- nanometer
- organic
- chainextender
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Silicon Polymers (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and a product thereof. The preparation method comprises the following steps: preparing raw materials of basic monomers, modified monomers and adjuvants; carrying out dewatering pretreatment on mixed polyether glycol; and carrying out pre-polymerization, chain extension, blocking, quaternization and emulsification. So the nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane is obtained. The method is easy to implement and control, and the nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane prepared by the method is in a microemulsion state, has a small and uniform emulsion particle size and a good dispersion, and combines merits of organic silicone, polyurethane and inorganic nanometer materials. So the polyurethane prepared in the invention, which can be used to improve the color fastness and pilling resistance of various dyed textiles, allows the textiles to have certain stain resistance, and soft feel of the textiles not to be damaged. Thereby the polyurethane has the advantages of good application performance, wide range of use, safety and environmental protection, and convenient usage.
Description
Technical field
The present invention relates to the dyefastness elevator that uses in the color fixing process behind the synthetic textile of the cotton type textiles of reactive dyestuffs, substantive dyestuff, vat dyes and sulfur dyeing and disperse dyeing, and contain the anti-pilling finishing agent that uses in the knitting finishing functions of textile fabrics of wool, cashmere and synthon, be specifically related to a kind of chemically active nanometer original position composite organic modified cation Synthesis of Waterborne Polyurethane method that has.
Background technology
At present, the aqueous polyurethane fastness to wet rubbing that often is used to various dyeing textile products improve and the anti-pilling finishing technology of various knitting textile products in.Aqueous polyurethane generally is by raw materials such as vulcabond and polyether glycol are made by body or solution polymerization and the processing method of carrying out self-emulsifying.
Above-mentioned raw materials comprises basic monomer, modified monomer and auxiliary, and wherein: basic monomer comprises polyether glycol, polyolefin diols, vulcabond, ionic chainextender, non-ionic type chainextender; Modified monomer comprises organoalkoxysilane coupling agent, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane; Auxiliary comprises basic monomer catalyzer, quaternizing agent, neutralizing agent, organic solvent, water etc.
The Synthesis of Waterborne Polyurethane method comprises following several at present:
1, the preparation method of organic-silicon-modified non-ionic polyurethane, its raw material comprises basic monomer, modified monomer and auxiliary, wherein: basic monomer comprises polyether glycol, vulcabond, non-ionic type chainextender; Modified monomer is the hydroxyl alkyl polysiloxane; Auxiliary comprises basic monomer catalyzer and organic solvent.
Show the preparation method of disclosed organic silicon modified polyurethane of " the synthetic and performance of organic silicon modified polyurethane " (" textile journal " 2009 30 the 10th phases of volume) as people such as Guo Yunfei, Bao Lihong, Liu Zhendong, in its raw material: basic monomer is that molecular weight is 1000 polypropylene glycol, isophorone diisocyanate, nonionic chainextender 1,4-butyleneglycol and TriMethylolPropane(TMP); Modified monomer is that molecular weight is 2000 hydroxyl-terminated injecting two methyl siloxane; Auxiliary is organic solvent butanone, butylacetate and catalyzer dibutyl tin laurate.
Although non-ionic organic silicon modified polyurethane has excellent water tolerance and compatibleness,, cause use inconvenience or effect not good enough because its wetting ability extreme difference is difficult for disperseing and being difficult for being emulsifiable in aqueous phase.In addition, the organic silicon modified polyurethane of this method preparation lacks chemically reactive, molecular weight is bigger, and adopts the small molecules of higher density crosslinked, therefore is not suitable for the production and the processing of textile printing and dyeing product.
2, the preparation method of organic-silicon-modified anion aqueous polyurethane, its raw material comprises basic monomer, modified monomer and auxiliary, wherein: basic monomer comprises polyether glycol, vulcabond, ionic chainextender; Modified monomer is ammonia alkyl polysiloxane or organoalkoxysilane coupling agent; Auxiliary comprises neutralizing agent, water etc.
Show the preparation method of disclosed organic silicon modified aqueous polyurethane of " development of organic silicon modified aqueous polyurethane emulsion " (" polyurethane industrial " 2005 20 the 1st phases of volume) as Hou Menghua, Liu Weiqu and Chen Jinghua, in its raw material: basic monomer is that molecular weight is 1000 polyoxypropyleneglycol, tolylene diisocyanate, negatively charged ion chainextender 2, the 2-dimethylol propionic acid; Modified monomer is aminoethyl aminopropyl polydimethylsiloxane, α, a kind of in the end capped polydimethylsiloxane of ω-two aminopropyl, the γ-An Jibingjisanyiyangjiguiwan; Auxiliary is neutralizing agent triethylamine and deionized water.
Although adopt organic silicon modified aqueous polyurethane can improve the mechanical property and the surface hydrophobicity of urethane, can be applicable to improve the anti-fluffing and anti-pilling performance of the colour fastness and the knitting textiles of dyed textiles, but because with 2, the 2-dimethylol propionic acid is a chainextender, its strong anionic property is difficult at fiber surface generation oriented adsorption polyurethane macromolecular, cause consumption bigger usually, and obviously cause the decline of textile product softness characteristics.In addition, the common molecular weight of the aqueous polyurethane of non-activity is bigger, also is unfavorable for diffusion and the absorption of macromole to the fiber microgap.
3, the preparation method of the organic-silicon-modified cation aqueous polyurethane of response type, its raw material comprises basic monomer, modified monomer and auxiliary, wherein: basic monomer comprises polyolefin diols, vulcabond, ionic chainextender, nonionic chainextender; Modified monomer is hydroxyl alkyl polysiloxane, organoalkoxysilane coupling agent; Auxiliary comprises quaternizing agent, neutralizing agent, organic solvent, water etc.
Such as Yang Wentang, Yan Qiao, Tang Li etc. the preparation method of work " cation aqueous polyurethane FS20566M " (" polyurethane industrial " 2009 24 volume the 5th phase) the organic-silicon-modified cation aqueous polyurethane of disclosed response type, in its raw material: basic monomer is polybutadiene diol, isoflurane chalcone diisocyanate, ionic chainextender N methyldiethanol amine, non-ionic type chainextender TriMethylolPropane(TMP); Modified monomer is end hydroxyalkyl modified polyorganosiloxane, aminopropyl trimethoxysilane; Auxiliary is quaternizing agent methyl iodide, neutralizing agent acetic acid, organic solvent N-Methyl pyrrolidone, deionized water.
This method is that flexible polyurethane monomer and the trifunctional small molecule monomer TriMethylolPropane(TMP) that adopts non-ionic type are chainextender with not hydrophilic fully polybutadiene diol, causes product to be difficult for emulsification, and emulsion particle diameter is big, size distribution broad and stability are not high; Because product is selected the hydrophilic restriction of monomer for use, macromole has the intramolecular crosslinking of higher density in addition, and it has the strong cation characteristic inevitable requirement.More than 2 make that this modified polyurethane macromole can not be with bigger quantity to fiber diffusion and absorption, and this point is most important for the lifting or the improvement of knitting textiles anti-fluffing and anti-pilling performance of DYED FABRICS colour fastness.
Summary of the invention
Technical problem to be solved by this invention is: preparation method of the organic-silicon-modified cation aqueous polyurethane of a kind of nanometer original position composite reaction-type and products thereof is provided.Easy to implement and the control of this method, the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type with this method preparation is the microemulsion state, good dispersion, combine the advantage of organosilicon, urethane and inorganic nano material, can be used for improving the anti-fluffing and anti-pilling performance of the colour fastness and the various knitting textiless of various dyeing textile products, and give textiles certain contamination resistance energy, and do not damage the soft feel of textiles.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
The preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type is characterized in that: may further comprise the steps:
(1) prepares raw material: basic monomer, modified monomer and auxiliary; Wherein: basic monomer comprises admixtured polyether glycol, vulcabond, ionic chainextender, non-ionic type chainextender; Modified monomer comprises organoalkoxysilane coupling agent, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, inorganic nanometer powder; Auxiliary comprises basic monomer catalyzer, reaction terminating agent, quaternizing agent, neutralizing agent, organic solvent, water;
The admixtured polyether glycol is that molecular weight is that 1000～3000 polyoxyethylene glycol and molecular weight are that 1000～3000 polypropylene glycol, molecular weight are that 1000～3000 end polyoxyethylene groups polypropylene glycol, molecular weight are that 1000～3000 ethylene oxide and propylene oxide block copolymerization glycol, molecular weight are that 1000～3000 polytetrahydrofuran diol, molecular weight are 1000～3000 tetrahydrofuran (THF) and a kind of combination in the ethylene oxide copolymerization glycol;
Vulcabond is a kind of in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, the dicyclohexyl methane diisocyanate;
The ionic chainextender is a kind of in trolamine, N butyl diethanol amine, the N-phenyldiethanol-amine;
The non-ionic type chainextender is 1,4-butyleneglycol, propylene glycol, 1, a kind of in 6-hexylene glycol, the quadrol;
The organoalkoxysilane coupling agent is a kind of in γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, 3-mercaptopropyltriethoxysilane, the γ-aminopropyl methyldiethoxysilane;
The hydroxyl alkyl polysiloxane is that molecular weight is 1000～3000 hydroxyl alkyl-terminated polydimethylsiloxane;
Ammonia alkyl polysiloxane is that molecular weight is 1000～3000 α, ω-two aminopropyl end-blocking polydimethylsiloxane;
A kind of in inorganic nanometer powder nano titanium oxide, nano silicon, the nano zine oxide;
The basic monomer catalyzer is stannous octoate or dibutyl tin laurate;
Reaction terminating agent is methyl alcohol or ethanol;
Quaternizing agent is a kind of in Benzyl Chloride, methylcarbonate, methyl-sulfate, n-butyl bromide, bromo pentane silane, the bromohexane;
Neutralizing agent is formic acid or acetate;
Organic solvent is a kind of in acetone, methylethylketone, vinyl acetic monomer, the N-BUTYL ACETATE;
The molfraction of each component is: vulcabond 1, admixtured polyether glycol 0.1～0.3, ionic chainextender 0.3～0.5, non-ionic type chainextender 0.1～0.2, hydroxyl alkyl polysiloxane 0～0.1, ammonia alkyl polysiloxane 0～0.1, organoalkoxysilane coupling agent 0.2～0.6, quaternizing agent 0.2～0.5, admixtured polyether glycol wherein, the ionic chainextender, the non-ionic type chainextender, the hydroxyl alkyl polysiloxane, the adduction of the molfraction of ammonia alkyl polysiloxane is no more than 0.9, and the molfraction of organoalkoxysilane coupling agent is (a 1-(admixtured polyether glycol+ionic chainextender+non-ionic type chainextender+hydroxyl alkyl polysiloxane+ammonia alkyl polysiloxane)) * 2;
Inorganic nanometer powder be the basic monomer gross weight 0.5～3%, the basic monomer catalyzer be the basic monomer gross weight 0.05～0.2%, reaction terminating agent be the basic monomer gross weight 0.5～2%, neutralizing agent is 60～100% of ionic chainextender weight;
The consumption of organic solvent is for can make emulsification normally get final product;
The consumption of water is that the solid content of adjustable product is not less than 20%;
(2) step of admixtured polyether diol dehydratase, this step is with the pre-treatment of dewatering under vacuum, heating condition of admixtured polyether glycol;
(3) step of pre-polymerization, admixtured polyether glycol, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, the inorganic nanometer powder of this step after with processed carries out prepolymerization reaction, makes nanometer original position composite organic modified polyurethane prepolymer;
(4) step of chain extension, this step is carried out chain extending reaction with nanometer original position composite organic modified polyurethane prepolymer, ionic chainextender, non-ionic type chainextender, makes nanometer original position composite organic modified polyurethane intermediate;
(5) end capped step, this step is carried out end capping with nanometer original position composite organic modified polyurethane intermediate, organoalkoxysilane coupling agent, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane;
(6) quaternised step, this step is carried out quaterisation with tertiary amine-type nanometer original position compounding machine silicon modified polyurethane, quaternizing agent, makes quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane;
(7) emulsive step, this step is mixed quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane, reaction terminating agent, neutralizing agent, organic solvent, water and emulsification, makes the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
In the such scheme, step (2) is specially:
(2.1) the admixtured polyether glycol is dropped into reactor;
(2.2) be heated to 100～120 ℃, in be not less than-handle 60～120min under the vacuum tightness of 0.01MPa.
In the such scheme, step (3) is specially:
(3.1) reaction system with step (2.2) is cooled to 60～80 ℃;
(3.2) drop into hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, inorganic nanometer powder, keep and stir 5～30min;
(3.3) heat temperature raising and keep stirring under 80～100 ℃, insulation reaction 120～200min makes nanometer original position composite organic modified polyurethane prepolymer.
In the such scheme, step (4) is specially:
(4.1) reaction system with step (3.3) is cooled to 40～60 ℃;
(4.2) the even mixture that drops into ionic chainextender and non-ionic type chainextender in 40～80min, keeping temperature of reaction is 50～70 ℃;
(4.3) continuing to keep temperature of reaction is 50～70 ℃, and continues stirring reaction 40～80min, makes nanometer original position composite organic modified polyurethane intermediate.
In the such scheme, step (5) is specially:
(5.1) reaction system with step (4.3) is cooled to 30～50 ℃;
(5.2) evenly drop into the organoalkoxysilane coupling agent in 10～30min, keeping temperature of reaction is 40～60 ℃;
(5.3) continuing to keep temperature of reaction is 40～60 ℃, and continues stirring reaction 20～40min, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane.
In the such scheme, step (6) is specially:
(6.1) reaction system with step (5.3) is warming up to 50～70 ℃;
(6.2) add quaternizing agent, and keep 50～70 ℃ of reaction 20～70min, make quaternary ammonium type nanometer original position composite organic modified polyurethane.
In the such scheme, step (7) is specially:
(7.1) stop heating, in the reaction system of step (6.2), add reaction terminating agent, and keep and stir 0～10min;
(7.2) add organic solvent, and be cooled to below 50 ℃;
(7.3) add neutralizing agent, and keep and stir 2～10min;
(7.4) improve the stirrer rotating speed, add entry several times;
(7.5) leave standstill, deaeration, make the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
Compared with prior art, the inventive method has the following advantages:
1, the inventive method is with inorganic nano material in-situ polymerization modified cation aqueous polyurethane, not only guaranteed the dispersion state that nano material is good to greatest extent, and when improving urethane epithelium wear resistance and mechanical property, also give its certain uvioresistant, multi-functional such as anti-contamination.
In numerous macromolecular materials, nano material and aqueous polyurethane have obviously consistency preferably, and unique effect such as it is antibiotic, refuse water, antifouling, uvioresistant can farthest be embodied in aqueous polyurethane dispersing liquid.Utilize the aqueous polyurethane dispersing characteristic good, the adhesion property of textiles excellence is transferred to nano material on the textiles securely, to realize the multiple function of textiles by urethane to nano material.
2, the inventive method is the main polymerization single polymerization monomer of urethane with hydrophilic admixtured polyether glycol, and does not introduce cross-linking type chainextender TriMethylolPropane(TMP).Reach adjustment by selection, proportioning, guaranteed that not only product has good film-forming properties, and product is easy to emulsification, emulsion particle diameter is less and size distribution is narrower the active termination ratio to different polyether glycols.In addition, the inventive method adopts ionic chainextender and non-ionic type chainextender that base polyurethane prepolymer for use as is carried out chain extending reaction simultaneously, can effectively regulate the positively charged ion intensity of product.
3, the product of the inventive method preparation is the molecular compound macromolecular material of the two modifications of a kind of nanometer/organosilicon.This molecular composite material combines the advantage of organosilicon, two kinds of macromolecular materials of urethane and inorganic nano material, with it textiles is carried out processing treatment, can not worsen the soft style of textile product, has excellent application performance energy and broad purposes.
4, the inventive method takes methods such as organic block copolymerization, chemical graft, active termination that cation aqueous polyurethane is carried out the organosilicon chemical modification, on cation aqueous polyurethane, introduced chemical in crosslinked and chemically reactive, and adopt in the in-situ polymerization normal direction modified polyurethane material and introduce inorganic nano material, fusion more between organosilicon and the polyurethane component microcell in the product of preparation, site size are littler, and inorganic nano material can farthest keep its primary characteristic.
5, the product of the inventive method preparation is the less polymer oligopolymer of a kind of molecular weight, has the cationic of higher chemically reactive and appropriateness, is easy to textile fibres diffusion, absorption and crosslinked thereon film forming, and is therefore low-consuming, effective.
6, the easy to implement and control of the inventive method, products production need not to change existing Synthesis of Waterborne Polyurethane technology and production unit, and product is the microemulsion form, safety and environmental protection, easy to use.
Embodiment
The preparation method of the organic-silicon-modified cation aqueous polyurethane of embodiment 1 nanometer original position composite reaction-type of the present invention
This preparation method's raw material comprises:
1, basic monomer
The admixtured polyether glycol: molecular weight is 3000 polyoxyethylene glycol 0.1 mol(300 g), molecular weight is 2000 polypropylene glycol 0.15 mol(300 g)
Vulcabond: isophorone diisocyanate 1.0 mol(222.3 g)
Ionic chainextender: N-phenyldiethanol-amine 0.5mol(90.6 g)
The non-ionic type chainextender: 1,4-butyleneglycol 0.1 mol(9.0 g)
2, modified monomer
Inorganic nanometer powder: nano silicon 9.2 g
The hydroxyl alkyl polysiloxane: molecular weight is 1000 hydroxyl alkyl-terminated polydimethylsiloxane 0.05 mol(50.0 g)
Ammonia alkyl polysiloxane: 0 mol(0 g)
Organoalkoxysilane coupling agent: 3-mercaptopropyltriethoxysilane 0.2 mol(47.7 g)
3, auxiliary
Basic monomer catalyzer: stannous octoate 1.0 g
Reaction terminating agent: ethanol 8.0 g
Quaternizing agent: bromo pentane silane 0.5 mol(75.5 g)
Neutralizing agent: acetate 63.4 g
Organic solvent: acetone 650 g
Water: 2600 g
This preparation method's concrete steps:
(1) step of admixtured polyether diol dehydratase, this step is with the pre-treatment of dewatering under vacuum, heating condition of admixtured polyether glycol; Be specially:
(1.1) polyoxyethylene glycol and polypropylene glycol are dropped into reactor;
(1.2) be heated to 100～105 ℃, in be not less than-handle 60min under the vacuum tightness of 0.01MPa.
(2) step of pre-polymerization, admixtured polyether glycol, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, the inorganic nanometer powder of this step after with processed carries out prepolymerization reaction, makes nanometer original position composite organic modified polyurethane prepolymer; Be specially:
(2.1) reaction system with step (1.2) is cooled to 60～65 ℃;
(2.2) the input molecule amount is 1000 the inferior tin of hydroxyl alkyl-terminated polydimethylsiloxane, isophorone diisocyanate, basic monomer octoate catalyst, inorganic nanometer powder nano silicon, keeps and stirs 6min;
(2.3) heat temperature raising and keep stirring under 80～85 ℃, insulation reaction 180min makes nanometer original position composite organic modified polyurethane prepolymer.
(3) step of chain extension, this step is carried out chain extending reaction with nanometer original position composite organic modified polyurethane prepolymer, ionic chainextender, non-ionic type chainextender, makes nanometer original position composite organic modified polyurethane intermediate; Be specially:
(3.1) reaction system with step (2.3) is cooled to 40～45 ℃;
(3.2) in 50min, evenly drop into ionic chainextender N-phenyldiethanol-amine and non-ionic type chainextender 1, the mixture of 4-butyleneglycol, keeping temperature of reaction is 50～55 ℃;
(3.3) continuing to keep temperature of reaction is 50～55 ℃, and continues stirring reaction 50min, makes nanometer original position composite organic modified polyurethane intermediate.
(4) end capped step, this step is carried out end capping with nanometer original position composite organic modified polyurethane intermediate, organoalkoxysilane coupling agent, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(4.1) reaction system with step (3.3) is cooled to 30～35 ℃;
(4.2) evenly drop into the 3-mercaptopropyltriethoxysilane in 15min, keeping temperature of reaction is 40～45 ℃;
(4.3) continuing to keep temperature of reaction is 40～45 ℃, and continues stirring reaction 25min, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane.
(5) quaternised step, this step is carried out quaterisation with tertiary amine-type nanometer original position compounding machine silicon modified polyurethane, quaternizing agent, makes quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(5.1) reaction system with step (4.3) is warming up to 50～55 ℃;
(5.2) add the quaternizing agent bromo pentane silane, and keep 50～55 ℃ of reaction 30min, make quaternary ammonium type nanometer original position composite organic modified polyurethane.
(6) emulsive step, this step is mixed quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane, reaction terminating agent, neutralizing agent, organic solvent, water and emulsification, makes the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type, is specially:
(6.1) stop heating, in the reaction system of step (5.2), add reaction terminating agent ethanol, and keep and stir 3min;
(6.2) add organic solvent-acetone, and be cooled to below 50 ℃;
(6.3) add neutralizing agent acetate, and keep and stir 3min;
(6.4) improve the stirrer rotating speed, add entry several times;
(6.5) leave standstill, deaeration, make solid content and be 25% the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
The end-use usage of the inventive method preparation:
Can be used for the back fixation treatment (the fastness to wet rubbing grade of handling the back textiles promotes and is not less than 1.0 grades) of the synthetic textile of the cotton type textiles of reactive dyestuffs, substantive dyestuff, vat dyes and sulfur dyeing and disperse dyeing and contain the anti-pilling finishing (the anti-fluffing and anti-pilling grade of handling the back textiles promotes and is not less than 1.5 grades) of the knitting textiles of wool, cashmere or synthon.
The product stock of the inventive method preparation:
Finished product must be located in the cool place, and sealing is preserved.
The preparation method of the organic-silicon-modified cation aqueous polyurethane of embodiment 2 nanometer original position composite reaction-types of the present invention
This preparation method's raw material comprises:
1, basic monomer
The admixtured polyether glycol: 2000 molecular weight polyethylene glycol, 0.1 mol(200 g), the polytetrahydrofuran diol 0.1 mol(300 g of 3000 molecular weight)
Vulcabond: hexamethylene diisocyanate 1.0 mol(168.2 g)
Ionic chainextender: N butyl diethanol amine 0.4mol(64.5 g)
The non-ionic type chainextender: 1,6-hexylene glycol 0.15 mol(17.7 g)
2, modified monomer
Inorganic nanometer powder: nano titanium oxide 13.0 g
Hydroxyl alkyl polysiloxane: 0 mol(0 g)
Ammonia alkyl polysiloxane: molecular weight is 2000 α, ω-two aminopropyl end-blocking polydimethylsiloxane 0.05 mol(100.0 g)
Organoalkoxysilane coupling agent: N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan 0.4 mol(105.8 g)
3, auxiliary
Basic monomer catalyzer: dibutyl tin laurate 0.8 g
Reaction terminating agent: ethanol 8.0 g
Quaternizing agent: n-butyl bromide 0.36 mol(49.3 g)
Neutralizing agent: acetate 60.0 g
Organic solvent: methylethylketone 600 g
Water: 2400 g
This preparation method's concrete steps:
(1) step of admixtured polyether diol dehydratase, this step is with the pre-treatment of dewatering under vacuum, heating condition of admixtured polyether glycol; Be specially:
(1.1) polyoxyethylene glycol and polytetrahydrofuran diol are dropped into reactor;
(1.2) be heated to 110～115 ℃, in be not less than-handle 100min under the vacuum tightness of 0.01MPa.
(2) step of pre-polymerization, admixtured polyether glycol, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, the inorganic nanometer powder of this step after with processed carries out prepolymerization reaction, makes nanometer original position composite organic modified polyurethane prepolymer; Be specially:
(2.1) reaction system with step (1.2) is cooled to 70～75 ℃;
(2.2) the input molecule amount is 2000 α, and ω-two aminopropyl end-blocking polydimethylsiloxane, hexamethylene diisocyanate, basic monomer catalyzer dibutyl tin laurate, inorganic nanometer powder nano titanium oxide are kept and stirred 20min;
(2.3) heat temperature raising and keep stirring under 90～95 ℃, insulation reaction 120min makes nanometer original position composite organic modified polyurethane prepolymer.
(3) step of chain extension, this step is carried out chain extending reaction with nanometer original position composite organic modified polyurethane prepolymer, ionic chainextender, non-ionic type chainextender, makes nanometer original position composite organic modified polyurethane intermediate; Be specially:
(3.1) reaction system with step (2.3) is cooled to 50～55 ℃;
(3.2) in 60min, evenly drop into ionic chainextender N butyl diethanol amine and non-ionic type chainextender 1, the mixture of 6-hexylene glycol, keeping temperature of reaction is 60～65 ℃;
(3.3) continuing to keep temperature of reaction is 60～65 ℃, and continues stirring reaction 60min, makes nanometer original position composite organic modified polyurethane intermediate.
(4) end capped step, this step is carried out end capping with nanometer original position composite organic modified polyurethane intermediate, organoalkoxysilane coupling agent, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(4.1) reaction system with step (3.3) is cooled to 40～45 ℃;
(4.2) evenly drop into organoalkoxysilane coupling agent N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan in 20min, keeping temperature of reaction is 40～45 ℃;
(4.3) continuing to keep temperature of reaction is 40～45 ℃, and continues stirring reaction 30min, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane.
(5) quaternised step, this step is carried out quaterisation with tertiary amine-type nanometer original position compounding machine silicon modified polyurethane, quaternizing agent, makes quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(5.1) reaction system with step (4.3) is warming up to 60～65 ℃;
(5.2) add the quaternizing agent n-butyl bromide, and keep 60～65 ℃ of reaction 40min, make quaternary ammonium type nanometer original position composite organic modified polyurethane.
(6) emulsive step, this step is mixed quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane, reaction terminating agent, neutralizing agent, organic solvent, water and emulsification, makes the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type, is specially:
(6.1) stop heating, in the reaction system of step (5.2), add reaction terminating agent ethanol, and keep and stir 10min;
(6.2) add the organic solvent methylethylketone, and be cooled to below 50 ℃;
(6.3) add neutralizing agent acetate, and keep and stir 6min;
(6.4) improve the stirrer rotating speed, add entry several times;
(6.5) leave standstill, deaeration, make solid content and be 25% the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
The end-use usage of the inventive method preparation:
Can be used for the cotton type textiles of reactive dyestuffs, substantive dyestuff, vat dyes and sulfur dyeing and disperse dyeing synthetic textile back fixation treatment and contain the anti-pilling finishing of the knitting textiles of wool, cashmere or synthon.
The product stock of the inventive method preparation:
Finished product must be located in the cool place, and sealing is preserved.
The preparation method of the organic-silicon-modified cation aqueous polyurethane of embodiment 3 nanometer original position composite reaction-types of the present invention
This preparation method's raw material comprises:
1, basic monomer
The admixtured polyether glycol: molecular weight is 2000 polyoxyethylene glycol 0.05mol(100g) and molecular weight be 2000 end polyoxyethylene groups polypropylene glycol 0.05mol(100g)
Vulcabond: tolylene diisocyanate 1.0 mol(174.2g)
Ionic chainextender: trolamine 0.3mol(44.8g)
Non-ionic type chainextender: propylene glycol 0.2mol(15.2g)
2, modified monomer
Inorganic nanometer powder: nano silicon 13g
The hydroxyl alkyl polysiloxane: molecular weight is 2000 hydroxyl alkyl-terminated polydimethylsiloxane 0.1mol(200g)
Ammonia alkyl polysiloxane: molecular weight is 3000 α, ω-two aminopropyl end-blocking polydimethylsiloxane 0.1 mol(300g)
Organoalkoxysilane coupling agent: γ-An Bingjisanyiyangjiguiwan 0.4 mol(88.6g)
3, auxiliary
Basic monomer catalyzer: dibutyl tin laurate 0.8g
Reaction terminating agent: ethanol 8.6g
Quaternizing agent: Benzyl Chloride 0.2mol(25.3g)
Neutralizing agent: formic acid 29.1g
Organic solvent: vinyl acetic monomer 650 g
Water: 2500 g
This preparation method's concrete steps:
(1) step of admixtured polyether diol dehydratase, this step is with the pre-treatment of dewatering under vacuum, heating condition of admixtured polyether glycol; Be specially:
(1.1) the admixtured polyether glycol is dropped into reactor;
(1.2) be heated to 110～115 ℃, in be not less than-handle 100min under the vacuum tightness of 0.01MPa.
(2) step of pre-polymerization, admixtured polyether glycol, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, the inorganic nanometer powder of this step after with processed carries out prepolymerization reaction, makes nanometer original position composite organic modified polyurethane prepolymer; Be specially:
(2.1) reaction system with step (1.2) is cooled to 70～75 ℃;
(2.2) drop into hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, inorganic nanometer powder, keep and stir 20min;
(2.3) heat temperature raising and keep stirring under 90～95 ℃, insulation reaction 120min makes nanometer original position composite organic modified polyurethane prepolymer.
(3) step of chain extension, this step is carried out chain extending reaction with nanometer original position composite organic modified polyurethane prepolymer, ionic chainextender, non-ionic type chainextender, makes nanometer original position composite organic modified polyurethane intermediate; Be specially:
(3.1) reaction system with step (2.3) is cooled to 50～55 ℃;
(3.2) the even mixture that drops into ionic chainextender and non-ionic type chainextender in 60min, keeping temperature of reaction is 60～65 ℃;
(3.3) continuing to keep temperature of reaction is 60～65 ℃, and continues stirring reaction 60min, makes nanometer original position composite organic modified polyurethane intermediate.
(4) end capped step, this step is carried out end capping with nanometer original position composite organic modified polyurethane intermediate, organoalkoxysilane coupling agent, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(4.1) reaction system with step (3.3) is cooled to 40～45 ℃;
(4.2) evenly drop into the organoalkoxysilane coupling agent in 20min, keeping temperature of reaction is 40～45 ℃;
(4.3) continuing to keep temperature of reaction is 40～45 ℃, and continues stirring reaction 30min, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane.
(5) quaternised step, this step is carried out quaterisation with tertiary amine-type nanometer original position compounding machine silicon modified polyurethane, quaternizing agent, makes quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane; Be specially:
(5.1) reaction system with step (4.3) is warming up to 60～65 ℃;
(5.2) add quaternizing agent, and keep 60～65 ℃ of reaction 40min, make quaternary ammonium type nanometer original position composite organic modified polyurethane.
(6) emulsive step, this step is mixed quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane, reaction terminating agent, neutralizing agent, organic solvent, water and emulsification, makes the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type, is specially:
(6.1) stop heating, in the reaction system of step (5.2), add reaction terminating agent, and keep and stir 10min;
(6.2) add organic solvent, and be cooled to below 50 ℃;
(6.3) add neutralizing agent, and keep and stir 6min;
(6.4) improve the stirrer rotating speed, add entry several times;
(6.5) leave standstill, deaeration, make the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
The end-use usage of the inventive method preparation:
Can be used for the cotton type textiles of reactive dyestuffs, substantive dyestuff, vat dyes and sulfur dyeing and disperse dyeing synthetic textile back fixation treatment and contain the anti-pilling finishing of the knitting textiles of wool, cashmere or synthon.
The product stock of the inventive method preparation:
Finished product must be located in the cool place, and sealing is preserved.
The above only is a preferred embodiments of the present invention, in fact each cited concrete raw material of the present invention, and the bound of each raw material, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Therefore, above embodiment is not in order to restriction the present invention, and common variation that those skilled in the art carries out in the technical solution of the present invention scope and replacement all should be included in protection scope of the present invention.
Claims (8)
1. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type is characterized in that: may further comprise the steps:
(1) prepares raw material: basic monomer, modified monomer and auxiliary; Wherein: basic monomer comprises admixtured polyether glycol, vulcabond, ionic chainextender, non-ionic type chainextender; Modified monomer comprises organoalkoxysilane coupling agent, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, inorganic nanometer powder; Auxiliary comprises basic monomer catalyzer, reaction terminating agent, quaternizing agent, neutralizing agent, organic solvent, water;
The admixtured polyether glycol is that molecular weight is that 1000～3000 polyoxyethylene glycol and molecular weight are that 1000～3000 polypropylene glycol, molecular weight are that 1000～3000 end polyoxyethylene groups polypropylene glycol, molecular weight are that 1000～3000 ethylene oxide and propylene oxide block copolymerization glycol, molecular weight are that 1000～3000 polytetrahydrofuran diol, molecular weight are 1000～3000 tetrahydrofuran (THF) and a kind of combination in the ethylene oxide copolymerization glycol;
Vulcabond is a kind of in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, the dicyclohexyl methane diisocyanate;
The ionic chainextender is a kind of in trolamine, N butyl diethanol amine, the N-phenyldiethanol-amine;
The non-ionic type chainextender is 1,4-butyleneglycol, propylene glycol, 1, a kind of in 6-hexylene glycol, the quadrol;
The organoalkoxysilane coupling agent is a kind of in γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanyiyangjiguiwan, 3-mercaptopropyltriethoxysilane, the γ-aminopropyl methyldiethoxysilane;
The hydroxyl alkyl polysiloxane is that molecular weight is 1000～3000 hydroxyl alkyl-terminated polydimethylsiloxane;
Ammonia alkyl polysiloxane is that molecular weight is 1000～3000 α, ω-two aminopropyl end-blocking polydimethylsiloxane;
A kind of in inorganic nanometer powder nano titanium oxide, nano silicon, the nano zine oxide;
The basic monomer catalyzer is stannous octoate or dibutyl tin laurate;
Reaction terminating agent is methyl alcohol or ethanol;
Quaternizing agent is a kind of in Benzyl Chloride, methylcarbonate, methyl-sulfate, n-butyl bromide, bromo pentane silane, the bromohexane;
Neutralizing agent is formic acid or acetate;
Organic solvent is a kind of in acetone, methylethylketone, vinyl acetic monomer, the N-BUTYL ACETATE;
The molfraction of each component is: vulcabond 1, admixtured polyether glycol 0.1～0.3, ionic chainextender 0.3～0.5, non-ionic type chainextender 0.1～0.2, hydroxyl alkyl polysiloxane 0～0.1, ammonia alkyl polysiloxane 0～0.1, organoalkoxysilane coupling agent 0.2～0.6, quaternizing agent 0.2～0.5, admixtured polyether glycol wherein, the ionic chainextender, the non-ionic type chainextender, the hydroxyl alkyl polysiloxane, the adduction of the molfraction of ammonia alkyl polysiloxane is no more than 0.9, and the molfraction of organoalkoxysilane coupling agent is (a 1-(admixtured polyether glycol+ionic chainextender+non-ionic type chainextender+hydroxyl alkyl polysiloxane+ammonia alkyl polysiloxane)) * 2;
Inorganic nanometer powder be the basic monomer gross weight 0.5～3%, the basic monomer catalyzer be the basic monomer gross weight 0.05～0.2%, reaction terminating agent be the basic monomer gross weight 0.5～2%, neutralizing agent is 60～100% of ionic chainextender weight;
The consumption of organic solvent is for can make emulsification normally get final product;
The consumption of water is that the solid content of adjustable product is not less than 20%;
(2) step of admixtured polyether diol dehydratase, this step is with the pre-treatment of dewatering under vacuum, heating condition of admixtured polyether glycol;
(3) step of pre-polymerization, admixtured polyether glycol, hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, the inorganic nanometer powder of this step after with processed carries out prepolymerization reaction, makes nanometer original position composite organic modified polyurethane prepolymer;
(4) step of chain extension, this step is carried out chain extending reaction with nanometer original position composite organic modified polyurethane prepolymer, ionic chainextender, non-ionic type chainextender, makes nanometer original position composite organic modified polyurethane intermediate;
(5) end capped step, this step is carried out end capping with nanometer original position composite organic modified polyurethane intermediate, organoalkoxysilane coupling agent, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane;
(6) quaternised step, this step is carried out quaterisation with tertiary amine-type nanometer original position compounding machine silicon modified polyurethane, quaternizing agent, makes quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane;
(7) emulsive step, this step is mixed quaternary ammonium type nanometer original position compounding machine silicon modified polyurethane, reaction terminating agent, neutralizing agent, organic solvent, water and emulsification, makes the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
2. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (2) is specially:
(2.1) the admixtured polyether glycol is dropped into reactor;
(2.2) be heated to 100～120 ℃, in be not less than-handle 60～120min under the vacuum tightness of 0.01MPa.
3. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (3) is specially:
(3.1) reaction system with step (2.2) is cooled to 60～80 ℃;
(3.2) drop into hydroxyl alkyl polysiloxane, ammonia alkyl polysiloxane, vulcabond, basic monomer catalyzer, inorganic nanometer powder, keep and stir 5～30min;
(3.3) heat temperature raising and keep stirring under 80～100 ℃, insulation reaction 120～200min makes nanometer original position composite organic modified polyurethane prepolymer.
4. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (4) is specially:
(4.1) reaction system with step (3.3) is cooled to 40～60 ℃;
(4.2) the even mixture that drops into ionic chainextender and non-ionic type chainextender in 40～80min, keeping temperature of reaction is 50～70 ℃;
(4.3) continuing to keep temperature of reaction is 50～70 ℃, and continues stirring reaction 40～80min, makes nanometer original position composite organic modified polyurethane intermediate.
5. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (5) is specially:
(5.1) reaction system with step (4.3) is cooled to 30～50 ℃;
(5.2) evenly drop into the organoalkoxysilane coupling agent in 10～30min, keeping temperature of reaction is 40～60 ℃;
(5.3) continuing to keep temperature of reaction is 40～60 ℃, and continues stirring reaction 20～40min, makes tertiary amine-type nanometer original position compounding machine silicon modified polyurethane.
6. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (6) is specially:
(6.1) reaction system with step (5.3) is warming up to 50～70 ℃;
(6.2) add quaternizing agent, and keep 50～70 ℃ of reaction 20～70min, make quaternary ammonium type nanometer original position composite organic modified polyurethane.
7. the preparation method of the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type according to claim 1 is characterized in that: step (7) is specially:
(7.1) stop heating, in the reaction system of step (6.2), add reaction terminating agent, and keep and stir 0～10min;
(7.2) add organic solvent, and be cooled to below 50 ℃;
(7.3) add neutralizing agent, and keep and stir 2～10min;
(7.4) improve the stirrer rotating speed, add entry several times;
(7.5) leave standstill, deaeration, make the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type.
8. the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type is characterized in that: it is that preparation method according to the organic-silicon-modified cation aqueous polyurethane of nanometer original position composite reaction-type in each claim among the claim 1-7 makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100926425A CN102199274B (en) | 2011-04-14 | 2011-04-14 | Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100926425A CN102199274B (en) | 2011-04-14 | 2011-04-14 | Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102199274A true CN102199274A (en) | 2011-09-28 |
| CN102199274B CN102199274B (en) | 2012-06-27 |
Family
ID=44660286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100926425A Expired - Fee Related CN102199274B (en) | 2011-04-14 | 2011-04-14 | Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199274B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505491A (en) * | 2011-11-01 | 2012-06-20 | 吴江市北厍盛源纺织品助剂厂 | Synthesizing method of polyurethane-modified organosilicon antimicrobial auxiliary agent |
| CN102619106A (en) * | 2012-04-16 | 2012-08-01 | 辽宁恒星精细化工有限公司 | Real leather suede leather stereoscopic printing paste and preparation method |
| CN103012731A (en) * | 2012-12-17 | 2013-04-03 | 青岛森淼实业有限公司 | Preparation method for waterborne polyurethane anti-pilling agent |
| CN103469594A (en) * | 2013-09-05 | 2013-12-25 | 东华大学 | Sorting method capable of improving anti-fuzzing performance of sung brocade fabric |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
| CN103497307A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof |
| CN104448208A (en) * | 2014-12-29 | 2015-03-25 | 中科院广州化学有限公司 | Organic silicon/nanometer ZnO composite modified polyurethane elastomer, preparation and application |
| CN104562703A (en) * | 2015-02-09 | 2015-04-29 | 苏州陈恒织造有限公司 | Wool fabric softening agent as well as preparation method thereof |
| CN104628988A (en) * | 2015-01-28 | 2015-05-20 | 东莞宝丽美化工有限公司 | Quaternary ammonium polyether solution and preparation method thereof |
| CN105063993A (en) * | 2015-08-06 | 2015-11-18 | 武汉纺织大学 | Method for enhancing stretching mechanical property of polyurethane fiber |
| CN105155346A (en) * | 2015-10-14 | 2015-12-16 | 南昌航空大学 | Preparation method for novel cation rosin surface sizing agent |
| CN107083682A (en) * | 2017-05-22 | 2017-08-22 | 苏州凯邦生物技术有限公司 | A kind of ventilating and moisture-permeable weaving water-proof aagent and preparation method thereof |
| CN108589276A (en) * | 2018-05-11 | 2018-09-28 | 河北多维康助剂有限公司 | A kind of preparation method and products thereof for the aqueous polyurethane textile finish that nano silver adulterates in situ |
| CN109679327A (en) * | 2018-12-26 | 2019-04-26 | 浙江东进新材料有限公司 | A kind of nano-organosilicon composite polyurethane water-proof emulsion |
| CN109721704A (en) * | 2019-01-11 | 2019-05-07 | 北京理工大学 | A kind of light shield extinguishing waterborn polyurethane and preparation method thereof |
| CN109760397A (en) * | 2018-12-25 | 2019-05-17 | 浙江东进新材料有限公司 | A kind of waterproof fabrics |
| CN110732804A (en) * | 2018-10-25 | 2020-01-31 | 嘉兴学院 | soldering flux for printing plate assembly and preparation method thereof |
| CN112281242A (en) * | 2020-11-12 | 2021-01-29 | 湖州欣缘纺织有限公司 | Preparation method of easy-to-dye chinlon organza fabric |
| CN112898529A (en) * | 2021-02-07 | 2021-06-04 | 武汉纺织大学 | Asymmetric star-shaped polyurethane thickener with cationic core and preparation method thereof |
| CN113279256A (en) * | 2021-07-01 | 2021-08-20 | 界首市华宇纺织有限公司 | Preparation method of anti-pilling wear-resistant yarn |
| CN113603858A (en) * | 2021-08-20 | 2021-11-05 | 上海涂固安高科技有限公司 | Water-based polymer inorganic composite nano-particles and application thereof |
| CN114232330A (en) * | 2021-11-22 | 2022-03-25 | 东华大学 | Application of nano silicon dioxide/waterborne polyurethane composite material |
| CN115012093A (en) * | 2022-07-05 | 2022-09-06 | 晋江康邦拓新材料科技有限公司 | Antibacterial and water-repellent fabric and processing method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077897A (en) * | 1997-12-01 | 2000-06-20 | Wen; Ten-Chin | Polymeric composite electrolyte and process for producing same |
| CN101164946A (en) * | 2007-09-20 | 2008-04-23 | 华明扬 | Preparing method of thermal insulation spraying agent for glass |
| CN101182682A (en) * | 2007-11-08 | 2008-05-21 | 华明扬 | Preparation method of textile water proof ventilating for medical and X-ray wave-absorbing coatings glue |
| CN101191304A (en) * | 2007-11-08 | 2008-06-04 | 华明扬 | Method for preparing anti-flaming water-proof ventilate wave-absorbing coating adhesive for military equipment outside covering textile |
| CN101481876A (en) * | 2008-01-31 | 2009-07-15 | 东莞市恩典皮具制品有限公司 | Aqueous polyurethane emulsion for synthetic leather and preparation thereof |
| CN101745271A (en) * | 2010-01-05 | 2010-06-23 | 江苏菲特滤料有限公司 | Compound photocatalysis antimicrobial air filter material and preparation method thereof |
| CN101805438A (en) * | 2010-04-13 | 2010-08-18 | 江苏工业学院 | Preparation method and applications of cationic waterborne polyurethane surface sizing agent |
| KR20100107328A (en) * | 2009-03-25 | 2010-10-05 | (주)다락 | Microsphere dispersed waterborne polyurethane and process for preparing the same |
-
2011
- 2011-04-14 CN CN2011100926425A patent/CN102199274B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077897A (en) * | 1997-12-01 | 2000-06-20 | Wen; Ten-Chin | Polymeric composite electrolyte and process for producing same |
| CN101164946A (en) * | 2007-09-20 | 2008-04-23 | 华明扬 | Preparing method of thermal insulation spraying agent for glass |
| CN101182682A (en) * | 2007-11-08 | 2008-05-21 | 华明扬 | Preparation method of textile water proof ventilating for medical and X-ray wave-absorbing coatings glue |
| CN101191304A (en) * | 2007-11-08 | 2008-06-04 | 华明扬 | Method for preparing anti-flaming water-proof ventilate wave-absorbing coating adhesive for military equipment outside covering textile |
| CN101481876A (en) * | 2008-01-31 | 2009-07-15 | 东莞市恩典皮具制品有限公司 | Aqueous polyurethane emulsion for synthetic leather and preparation thereof |
| KR20100107328A (en) * | 2009-03-25 | 2010-10-05 | (주)다락 | Microsphere dispersed waterborne polyurethane and process for preparing the same |
| CN101745271A (en) * | 2010-01-05 | 2010-06-23 | 江苏菲特滤料有限公司 | Compound photocatalysis antimicrobial air filter material and preparation method thereof |
| CN101805438A (en) * | 2010-04-13 | 2010-08-18 | 江苏工业学院 | Preparation method and applications of cationic waterborne polyurethane surface sizing agent |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505491A (en) * | 2011-11-01 | 2012-06-20 | 吴江市北厍盛源纺织品助剂厂 | Synthesizing method of polyurethane-modified organosilicon antimicrobial auxiliary agent |
| CN102619106A (en) * | 2012-04-16 | 2012-08-01 | 辽宁恒星精细化工有限公司 | Real leather suede leather stereoscopic printing paste and preparation method |
| CN103012731A (en) * | 2012-12-17 | 2013-04-03 | 青岛森淼实业有限公司 | Preparation method for waterborne polyurethane anti-pilling agent |
| CN103469594A (en) * | 2013-09-05 | 2013-12-25 | 东华大学 | Sorting method capable of improving anti-fuzzing performance of sung brocade fabric |
| CN103497307B (en) * | 2013-10-22 | 2015-05-20 | 武汉纺织大学 | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof |
| CN103497307A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof |
| CN103497308A (en) * | 2013-10-22 | 2014-01-08 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
| CN103497308B (en) * | 2013-10-22 | 2015-05-20 | 武汉纺织大学 | Low temperature high elastic type waterproof antifouling water-based polyurethane finishing agent preparing method and product |
| CN104448208A (en) * | 2014-12-29 | 2015-03-25 | 中科院广州化学有限公司 | Organic silicon/nanometer ZnO composite modified polyurethane elastomer, preparation and application |
| CN104448208B (en) * | 2014-12-29 | 2017-04-12 | 中科院广州化学有限公司 | Organic silicon/nanometer ZnO composite modified polyurethane elastomer, preparation and application |
| CN104628988A (en) * | 2015-01-28 | 2015-05-20 | 东莞宝丽美化工有限公司 | Quaternary ammonium polyether solution and preparation method thereof |
| CN104562703A (en) * | 2015-02-09 | 2015-04-29 | 苏州陈恒织造有限公司 | Wool fabric softening agent as well as preparation method thereof |
| CN105063993A (en) * | 2015-08-06 | 2015-11-18 | 武汉纺织大学 | Method for enhancing stretching mechanical property of polyurethane fiber |
| CN105155346A (en) * | 2015-10-14 | 2015-12-16 | 南昌航空大学 | Preparation method for novel cation rosin surface sizing agent |
| CN107083682A (en) * | 2017-05-22 | 2017-08-22 | 苏州凯邦生物技术有限公司 | A kind of ventilating and moisture-permeable weaving water-proof aagent and preparation method thereof |
| CN107083682B (en) * | 2017-05-22 | 2019-07-05 | 苏州凯邦生物技术有限公司 | A kind of ventilating and moisture-permeable weaving water-proof aagent and preparation method thereof |
| CN108589276B (en) * | 2018-05-11 | 2021-03-23 | 河北多维康助剂有限公司 | Preparation method of nano-silver in-situ doped waterborne polyurethane textile finishing agent and product thereof |
| CN108589276A (en) * | 2018-05-11 | 2018-09-28 | 河北多维康助剂有限公司 | A kind of preparation method and products thereof for the aqueous polyurethane textile finish that nano silver adulterates in situ |
| CN110732804A (en) * | 2018-10-25 | 2020-01-31 | 嘉兴学院 | soldering flux for printing plate assembly and preparation method thereof |
| CN109760397A (en) * | 2018-12-25 | 2019-05-17 | 浙江东进新材料有限公司 | A kind of waterproof fabrics |
| CN109679327A (en) * | 2018-12-26 | 2019-04-26 | 浙江东进新材料有限公司 | A kind of nano-organosilicon composite polyurethane water-proof emulsion |
| CN109679327B (en) * | 2018-12-26 | 2021-03-23 | 浙江东进新材料有限公司 | Nano organic silicon composite polyurethane waterproof emulsion |
| CN109721704A (en) * | 2019-01-11 | 2019-05-07 | 北京理工大学 | A kind of light shield extinguishing waterborn polyurethane and preparation method thereof |
| CN112281242A (en) * | 2020-11-12 | 2021-01-29 | 湖州欣缘纺织有限公司 | Preparation method of easy-to-dye chinlon organza fabric |
| CN112898529A (en) * | 2021-02-07 | 2021-06-04 | 武汉纺织大学 | Asymmetric star-shaped polyurethane thickener with cationic core and preparation method thereof |
| CN112898529B (en) * | 2021-02-07 | 2022-06-07 | 武汉纺织大学 | Asymmetric star-shaped polyurethane thickener with cationic core and preparation method thereof |
| CN113279256A (en) * | 2021-07-01 | 2021-08-20 | 界首市华宇纺织有限公司 | Preparation method of anti-pilling wear-resistant yarn |
| CN113603858A (en) * | 2021-08-20 | 2021-11-05 | 上海涂固安高科技有限公司 | Water-based polymer inorganic composite nano-particles and application thereof |
| CN114232330A (en) * | 2021-11-22 | 2022-03-25 | 东华大学 | Application of nano silicon dioxide/waterborne polyurethane composite material |
| CN115012093A (en) * | 2022-07-05 | 2022-09-06 | 晋江康邦拓新材料科技有限公司 | Antibacterial and water-repellent fabric and processing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102199274B (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102199274B (en) | Preparation method of nanometer in situ composite reaction type organic silicone modified cationic water-based polyurethane and product thereof | |
| CN105884999B (en) | Preparation method and products thereof containing hydrophilic and hydrophobic side long-chain modified cation aqueous polyurethane emulsion | |
| CN103497307B (en) | Preparation method of quaternary ammonium type positive ion polyurethane base polyether block hydrophilic silicone softener ultra-micro emulsion and product thereof | |
| CN104650363B (en) | Preparation method of hyperbranched ternary polymerization organic silicon | |
| CN111004395B (en) | Preparation method of low-solvent block type polyether amino silicone oil | |
| CN101581039B (en) | Durable antistatic finishing agent for fabrics and preparation method | |
| CN101768884B (en) | Multi-quaternary ammonium group cation type polyurethane color fixing agent and preparation method thereof | |
| KR970004930B1 (en) | Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings | |
| CA1241485A (en) | Process for the preparation of coating compositions, aqueous dispersions of pu reactive systems and their use for coating | |
| CN103147306A (en) | Textile anti-pilling polyurethane finishing agent and preparation method thereof | |
| CN101736619B (en) | Cation type reactive polyurethane coloring stabilizer and preparation method thereof | |
| CN109970945A (en) | A kind of organic-silicon-modified weak amphoteric ion type polyaminoester emulsion and preparation method thereof | |
| CN104744642B (en) | The preparation method of nano-titanium dioxide modified color-fixing agent emulsion | |
| CN101307180B (en) | Cationoid polyurethane and modified silicon oil composite water dispersion, preparation and applications | |
| CN108589276B (en) | Preparation method of nano-silver in-situ doped waterborne polyurethane textile finishing agent and product thereof | |
| CN106046316B (en) | A kind of preparation method and products thereof of the crosslinked tree-shaped cladodification cationic silicone microemulsion of low-density | |
| CN101302276A (en) | Preparation technology of soft highly-elastic fabric anti-fluffing anti-pilling finishing agent | |
| CN101818458B (en) | Preparation method of organosilicon modified polyurethane hyperchromic improver | |
| CN107814941A (en) | A kind of microwave preparation of the quaternized block organosilicon polymer of smooth type | |
| CN105622944A (en) | Quaternized organic silicone oil and preparation method thereof | |
| CN109403044B (en) | Preparation method of terylene hydrophilic antistatic finishing agent emulsion and product thereof | |
| CN105170019A (en) | Preparation method for cationic polyurethane macro-molecule surfactant | |
| CN104130376A (en) | Cationic organosilicon-modified polyurethane emulsion and preparation method thereof | |
| CN104878604A (en) | Preparation method of cation-type waterborne polyurethane wool anti-felting emulsion | |
| CN105755837A (en) | Preparation method and application of quaternization modified amino silicon oil softener |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB02 | Change of applicant information |
Inventor after: Quan Heng Inventor after: Kong Xiangfeng Inventor after: Wang Zhongjie Inventor after: Sun Qingcheng Inventor after: Meng Xiao Inventor after: Chen Jianping Inventor after: Li Qingwen Inventor after: Wu Guohua Inventor after: Tian Kaiwu Inventor before: Quan Heng Inventor before: Meng Xiao Inventor before: Chen Jianping Inventor before: Li Qingwen Inventor before: Wu Guohua Inventor before: Tian Kaiwu |
|
| CB03 | Change of inventor or designer information | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161221 Address after: 054899 Qinghe County cashmere products market in Hebei, Xingtai cashmere street, No. 8 Patentee after: Qinghe Cashmere Industry Technology Research Institute Address before: 430073 College of chemical engineering, Wuhan Textile University, Wuhan Road, Hongshan, Hubei, China Patentee before: Wuhan Textile University |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120627 Termination date: 20210414 |